Systems and methods for forming niobium and/or vanadium containing layers using atomic layer deposition

ABSTRACT

A method of forming (and an apparatus for forming) a metal containing layer on a substrate, particularly a semiconductor substrate or substrate assembly for use in manufacturing a semiconductor or memory device structure, using one or more precursor compounds that include niobium and/or vanadium and using an atomic layer deposition process including a plurality of deposition cycles.

FIELD OF THE INVENTION

This invention relates to methods of forming a metal containing layer,such as a metal oxide layer, on a substrate using one or more precursorcompounds using a vapor deposition process. The precursor compounds andmethods are particularly suitable for the formation of metal containinglayers on semiconductor substrates or substrate assemblies.

BACKGROUND OF THE INVENTION

In integrated circuit manufacturing, microelectronic devices such ascapacitors are the basic energy storage devices in random access memorydevices, such as dynamic random access memory (DRAM) devices, staticrandom access memory (SRAM) devices, and ferroelectric memory (FERAM)devices. Capacitors typically consist of two conductors, such asparallel metal or polysilicon plates, which act as the electrodes (i.e.,the storage node electrode and the cell plate capacitor electrode),insulated from each other by a layer of dielectric material.

The continuous shrinkage of microelectronic devices such as capacitorsand gates over the years has led to a situation where the materialstraditionally used in integrated circuit technology are approachingtheir performance limits. Silicon (i.e., doped polysilicon) hasgenerally been the substrate of choice, and silicon dioxide (SiO₂) hasfrequently been used as the dielectric material with silicon toconstruct microelectronic devices. However, when the SiO₂ layer isthinned to 1 nanometer (nm) (i.e., a thickness of only 4 or 5molecules), as is desired in the newest micro devices, the layer nolonger effectively performs as an insulator due to the tunneling currentrunning through it.

Thus, new high dielectric constant materials are needed to extend deviceperformance. Such materials need to demonstrate high permittivity,barrier height to prevent tunneling, stability in direct contact withsilicon, and good interface quality and film morphology. Furthermore,such materials must be compatible with the gate material, electrodes,semiconductor processing temperatures, and operating conditions.

High quality thin oxide films of metals, such as ZrO₂, Ta₂O₅, HfO₂,Al₂O₃, Nb₂O₅, and YSZ deposited on semiconductor wafers have recentlygained interest for use in memories (e.g., dynamic random access memory(DRAM) devices, static random access memory (SRAM) devices, andferroelectric memory (FERAM) devices). These materials have highdielectric constants and therefore are attractive as replacements inmemories for SiO₂ where very thin layers are required. These metal oxidelayers are thermodynamically stable in the presence of silicon,minimizing silicon oxidation upon thermal annealing, and appear to becompatible with metal gate electrodes. Additionally, Nb₂O₅, Nb₂O₅doped/laminated Al₂O₃, Ta₂O₅, and HfO₂ films have been shown to beuseful for capacitor and gate dielectrics. Nb₂O₅ doping/laminating hasbeen shown to decrease leakage and stabilize crystalline phases.

Efforts have been made to investigate various deposition processes toform layers, especially dielectric layers, based on metal oxides. Suchdeposition processes have included vapor deposition, metal thermaloxidation, and high vacuum sputtering. Vapor deposition processes, whichincludes chemical vapor deposition (CVD) and atomic layer deposition(ALD), are very appealing as they provide for excellent control ofdielectric uniformity and thickness on a substrate.

SUMMARY OF THE INVENTION

In view of the foregoing, and despite improvements in semiconductordielectric layers, there remains a need in the semiconductor art for avapor deposition process utilizing sufficiently volatile metal precursorcompounds that can form a thin, high quality oxide layer, particularlyon a semiconductor substrate. Accordingly, the present invention isdirected to methods of manufacturing a semiconductor structure includingat least one precursor compound including a metal selected from thegroup of niobium and vanadium, to methods of forming a niobium oxidelayer on a substrate, and to an atomic layer vapor deposition apparatusthat includes at least one precursor compound including a metal selectedfrom the group of niobium and vanadium.

In one aspect, the present invention is directed to a method ofmanufacturing a semiconductor structure, the method including: providinga semiconductor substrate or substrate assembly; providing a vaporincluding at least one precursor compound of the formulaM(OR¹)_(5-x)(XR²O)_(x) (Formula I), wherein M is selected from the groupconsisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or (OR⁵),each R¹, R², R³, R⁴, and R⁵ is independently an organic group, x=1 or 2;and contacting the vapor including the at least one precursor compoundof Formula I with the semiconductor substrate or substrate assembly toform a metal-containing layer on at least one surface of thesemiconductor substrate or substrate assembly using an atomic layerdeposition process including a plurality of deposition cycles.

The present invention may also include the use of a reaction gas inmethods for the manufacture of a semiconductor structure. Thus, in afurther aspect, the present invention is also directed to a method ofmanufacturing a semiconductor structure, the method including: providinga semiconductor substrate or substrate assembly; providing a vaporincluding at least one precursor compound of the formulaM(OR¹)_(5-x)(XR²O)_(x) (Formula I), wherein M is selected from the groupconsisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or (OR⁵),each R¹, R², R³, R⁴, and R⁵ is independently an organic group, x=1 or 2;providing at least one reaction gas; and contacting the vapor includingthe at least one precursor compound of Formula I with the semiconductorsubstrate or substrate assembly to form a metal-containing layer on atleast one surface of the semiconductor substrate or substrate assemblyusing an atomic layer deposition process including a plurality ofdeposition cycles.

In yet another aspect, the present invention is directed to a method ofmanufacturing a semiconductor structure, the method including: providinga semiconductor substrate or substrate assembly within a depositionchamber; providing a vapor including at least one precursor compound ofthe formula M(OR¹)_(5-x)(XR²O)_(x) (Formula I), wherein M is selectedfrom the group consisting of niobium and vanadium, X is (NR³R⁴),(PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ is independently anorganic group, x=1 or 2; directing the vapor including the at least oneprecursor compound of Formula I to the semiconductor substrate orsubstrate assembly and allowing the at least one compound to chemisorbto at least one surface of the semiconductor substrate or substrateassembly; providing at least one reaction gas; and directing the atleast one reaction gas to the semiconductor substrate or substrateassembly with the chemisorbed species thereon to form a metal-containinglayer on at least one surface of the semiconductor substrate orsubstrate assembly.

In certain applications, it may be advantageous to include deposition ofa metal-containing precursor composition in addition to, and differentfrom, the precursor composition of Formula I. To this end the presentinvention is further directed in yet another aspect to a method ofmanufacturing a semiconductor structure, the method including: providinga semiconductor substrate or substrate assembly; providing a vaporincluding at least one precursor compound of the formulaM(OR¹)_(5-x)(XR²O)_(x) (Formula I), wherein M is selected from the groupconsisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or (OR⁵),each R¹, R², R³, R⁴, and R⁵ is independently an organic group, x=1 or 2;providing a vapor including at least one metal-containing precursorcompound different than M(OR¹)_(5-x)(X(R²O)_(x) (Formula I); directingthe vapor including the at least one precursor compound of Formula I andthe vapor including the at least one metal-containing precursor compounddifferent that the precursor compound of Formula I to the semiconductorsubstrate or substrate assembly to form a metal-containing layer on atleast one surface of the semiconductor substrate or substrate assemblyusing an atomic layer deposition process including a plurality ofdeposition cycles.

It is further recognized that the present invention may be useful in theformation of a niobium oxide layer on any appropriate substrate for anyapplication wherein such a layer is desired. Thus, in another aspect thepresent invention is directed to a method of forming a niobium oxidelayer on a substrate, the method including: providing a substrate;providing a vapor including at least one precursor compound of theformula M(OR¹)_(5-x)(XR²O)_(x) (Formula I), wherein M is niobium, X is(NR³R⁴), (PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ is independentlyan organic group, x=1 or 2; and contacting the vapor including the atleast one precursor compound with the substrate to form a niobium oxidelayer on at least one surface of the substrate using an atomic layerdeposition process including a plurality of deposition cycles.

Additionally, the present invention contemplates the formation of aniobium oxide layer on a substrate including the use of a reaction gasin the method. Therefore, in yet a further aspect, the present inventionis directed to a method of forming a niobium oxide layer on a substrate,the method including: providing a substrate; providing a vapor includingat least one precursor compound of the formula M(OR¹)_(5-x)(XR²O)_(x)(Formula I), wherein M is niobium, X is (NR³R⁴), (PR³R⁴), or (OR⁵), eachR¹, R², R³, R⁴, and R⁵ is independently an organic group, x=1 or 2;providing at least one reaction gas; and contacting the vapor includingthe at least one precursor compound with the substrate to form a niobiumoxide layer on at least one surface of the substrate using an atomiclayer deposition process including a plurality of deposition cycles.

The present invention, in yet another aspect, is directed to a method offorming a niobium oxide layer on a substrate, the method including:providing a substrate within a deposition chamber; providing a vaporincluding at least one precursor compound of the formulaM(OR¹)_(5-x)(XR²O)_(x) (Formula I), wherein M is niobium, X is (NR³R⁴),(PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ is independently anorganic group, x=1 or 2; directing the vapor including the at least oneprecursor compound of Formula I to the substrate and allowing the atleast one compound to chemisorb to at least one surface of thesubstrate; providing at least one reaction gas; and directing the atleast one reaction gas to the substrate with the chemisorbed speciesthereon to form a niobium oxide layer on at least one surface of thesubstrate.

Methods of the present invention are also useful in the formation of aniobium oxide layer on a substrate where deposition of an additionalmetal-containing precursor is desired. To this end, in a further aspectthe present invention is directed to a method of forming a niobium oxidelayer on a substrate, the method including: providing a substrate;providing a vapor including at least one precursor compound of theformula M(OR¹)_(5-x)(XR²O)_(x) (Formula I), wherein M is niobium, X is(NR³R⁴), (PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ is independentlyan organic group, x=1 or 2; providing a vapor including at least onemetal-containing precursor compound different thanM(OR¹)_(5-x)(X(R²O)_(x) (Formula I); directing the vapor including theat least one precursor compound of Formula I and the vapor including theat least one metal-containing precursor compound different that theprecursor compound of Formula I to the substrate to form a layerincluding niobium oxide on at least one surface of the substrate usingan atomic layer deposition process including a plurality of depositioncycles.

Additionally, methods of the present invention may advantageously beused in the manufacture of memory devices. Thus, in yet a furtheraspect, the present invention is also directed to a method ofmanufacturing a memory device structure, the method including: providinga substrate having a first electrode thereon; providing at least oneprecursor compound of the formula M(OR¹)_(5-x)(XR²O)_(x) (Formula I),wherein M is selected from the group consisting of niobium and vanadium,X is (NR³R⁴), (PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ isindependently an organic group, x=1 or 2; vaporizing the at least oneprecursor compound of Formula I; contacting the at least one vaporizedprecursor compound of Formula I with the substrate to chemisorb thecompound on the first electrode of the substrate; providing at least onereaction gas; contacting the at least one reaction gas with thesubstrate with the chemisorbed compound thereon to form a dielectriclayer on the first electrode of the substrate; and forming a secondelectrode on the dielectric layer.

Further, the present invention also provides an apparatus useful for thedeposition of precursor compositions as taught herein. In yet anotheraspect, therefore, the present invention is directed to an atomic layervapor deposition apparatus including: a deposition chamber having asubstrate positioned therein; and at least one vessel including at leastone precursor compound of the formula M(OR¹)_(5-x)(XR²O)_(x) (FormulaI), wherein M is selected from the group consisting of niobium andvanadium, X is (NR³R⁴), (PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵is independently an organic group, and x=1 or 2.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a perspective view of a vapor deposition coating systemsuitable for use in the method of the present invention.

FIG. 2 is an exemplary capacitor construction formed using methods ofthe present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

The present invention includes a method of forming metal containinglayers, preferably metal oxide layers, on substrates, preferably byusing an atomic vapor deposition process and using one or more metalprecursor compounds, wherein metal is selected from the group of niobiumand vanadium. The atomic layer deposition process may, preferably,include a plurality of deposition cycles.

The terms “semiconductor substrate” or “substrate assembly” as usedherein refer to a semiconductor substrate such as a base semiconductorlayer or a semiconductor substrate having one or more layers,structures, or regions formed thereon. A base semiconductor layer istypically the lowest layer of silicon material on a wafer or a siliconlayer deposited on another material, such as silicon on sapphire. Whenreference is made to a substrate assembly, various process steps mayhave been previously used to form or define regions, junctions, variousstructures or features, and openings such as capacitor plates orbarriers for capacitors.

The term “layer” as used herein refers to any metal-containing layerthat can be formed on a substrate from the precursor compounds of thisinvention using a vapor deposition process. The term “layer” is meant toinclude layers specific to the semiconductor industry, such as “barrierlayer,” “dielectric layer,” and “conductive layer.” (The term “layer” issynonymous with the term “film” frequently used in the semiconductorindustry.) The term “layer” is also meant to include layers found intechnology outside of semiconductor technology, such as coatings onglass.

The terms “deposition process” and “vapor deposition process” as usedherein refer to a process in which a metal-containing layer is formed onone or more surfaces of a substrate (e.g., a doped polysilicon wafer)from vaporized precursor compound(s). Specifically, one or more metalprecursor compounds are vaporized and directed to and/or contacted withone or more surfaces of a heated substrate (e.g., semiconductorsubstrate or substrate assembly) placed in a deposition chamber. Theseprecursor compounds form (e.g., by reacting or decomposing) anon-volatile, thin, uniform, metal-containing layer on the surface(s) ofthe substrate. For the purposes of this invention, the term “vapordeposition process” is meant to include both chemical vapor depositionprocesses (including pulsed chemical vapor deposition processes) andatomic layer deposition processes.

The term “atomic layer deposition” (ALD) as used herein refers to avapor deposition process in which numerous consecutive deposition cyclesare conducted in a deposition chamber. Typically, during each cycle themetal precursor is chemisorbed to the substrate surface; excessprecursor is purged out; a subsequent precursor and/or reaction gas isintroduced to react with the chemisorbed layer; and excess reaction gas(if used) and by-products are removed. As compared to a typical chemicalvapor deposition (CVD) process wherein the desired layer is deposited ina single cycle onto the substrate from vaporized metal precursorcompounds (and any reaction gasses used) within a deposition chamber,the longer duration multi-cycle ALD process allows for improved controlof layer thickness by self-limiting layer growth and minimizingdetrimental gas phase reactions by separation of the reactioncomponents. The term “atomic layer deposition” as used herein is alsomeant to include the related terms “atomic layer epitaxy” (ALE),molecular beam epitaxy (MBE), gas source MBE, organometallic MBE, andchemical beam epitaxy when performed with alternating pulses ofprecursor compound(s), reaction gas(es), and purge (i.e., inert carrier)gas.

The term “chemisorption” as used herein refers to the chemicaladsorption of vaporized reactive precursor compounds on the surface of asubstrate. The adsorbed species are irreversibly bound to the substratesurface as a result of relatively strong binding forces characterized byhigh adsorption energies (e.g., >30 kcal/mol), comparable in strength toordinary chemical bonds. The chemisorbed species typically form amononolayer on the substrate surface. (See “The Condensed ChemicalDictionary”, 10th edition, revised by G. G. Hawley, published by VanNostrand Reinhold Co., New York, 225 (1981)). The technique of ALD isbased on the principle of the formation of a saturated monolayer ofreactive precursor molecules by chemisorption. In ALD one or moreappropriate precursor compounds or reaction gasses are alternatelyintroduced (e.g., pulsed) into a deposition chamber and chemisorbed ontothe surfaces of a substrate. Each sequential introduction of a reactivecompound (e.g., one or more precursor compounds and one or more reactiongasses) is typically separated by an inert carrier gas purge. Eachprecursor compound co-reaction adds a new atomic layer to previouslydeposited layers to form a cumulative solid layer. The cycle isrepeated, typically for several hundred times, to gradually form thedesired layer thickness. It should be understood that ALD canalternately utilize one precursor compound, which is chemisorbed, andone reaction gas, which reacts with the chemisorbed species.

The present invention includes methods of forming a metal containinglayer, preferably a metal oxide layer such as, for example, a niobiumoxide layer, on a substrate. Further, such metal containing layer ispreferably formed on a semiconductor substrate or substrate assembly inthe manufacture of a semiconductor structure or another memory devicestructure. Such layers are deposited or chemisorbed onto a substrate andform, preferably, dielectric layers. The methods of the presentinvention involve forming a layer on a substrate by using one or moremetal precursor compounds of the formula:M(OR¹)_(5-x)(XR²O)_(x)   (Formula I)wherein M is selected from niobium and vanadium, X is (NR³R⁴), (PR³R⁴),or (OR⁵), x is 1 or 2, and each R¹, R², R³, R⁴, and R⁵ is independentlyan organic group (as described in greater detail below). Additionally,the present invention includes methods of forming a metal containinglayer further including using a precursor compound in addition to anddifferent from the compound of Formula I. An apparatus useful for atomiclayer deposition (ALD, discussed more fully below) of the disclosedprecursor compounds is also disclosed.

As used herein, the term “organic group” is used for the purpose of thisinvention to mean a hydrocarbon group that is classified as an aliphaticgroup, cyclic group, or combination of aliphatic and cyclic groups(e.g., alkaryl and aralkyl groups). In the context of the presentinvention, suitable organic groups for precursor compounds of thisinvention are those that do not interfere with the formation of a metaloxide layer using vapor deposition techniques. In the context of thepresent invention, the term “aliphatic group” means a saturated orunsaturated linear or branched hydrocarbon group. This term is used toencompass alkyl, alkenyl, and alkynyl groups, for example. The term“alkyl group” means a saturated linear or branched monovalenthydrocarbon group including, for example, methyl, ethyl, n-propyl,isopropyl, t-butyl, amyl, heptyl, and the like. The term “alkenyl group”means an unsaturated, linear or branched monovalent hydrocarbon groupwith one or more olefinically unsaturated groups (i.e., carbon-carbondouble bonds), such as a vinyl group. The term “alkynyl group” means anunsaturated, linear or branched monovalent hydrocarbon group with one ormore carbon-carbon triple bonds. The term “cyclic group” means a closedring hydrocarbon group that is classified as an alicyclic group,aromatic group, or heterocyclic group. The term “alicyclic group” meansa cyclic hydrocarbon group having properties resembling those ofaliphatic groups. The term “aromatic group” or “aryl group” means amono- or polynuclear aromatic hydrocarbon group. The term “heterocyclicgroup” means a closed ring hydrocarbon in which one or more of the atomsin the ring is an element other than carbon (e.g., nitrogen, oxygen,sulfur, etc.).

As a means of simplifying the discussion and the recitation of certainterminology used throughout this application, the terms “group” and“moiety” are used to differentiate between chemical species that allowfor substitution or that may be substituted and those that do not soallow for substitution or may not be so substituted. Thus, when the term“group” is used to describe a chemical substituent, the describedchemical material includes the unsubstituted group and that group withnonperoxidic O, N, S, Si, or F atoms, for example, in the chain as wellas carbonyl groups or other conventional substituents. Where the term“moiety” is used to describe a chemical compound or substituent, only anunsubstituted chemical material is intended to be included. For example,the phrase “alkyl group” is intended to include not only pure open chainsaturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl,t-butyl, and the like, but also alkyl substituents bearing furthersubstituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl,halogen atoms, cyano, nitro, amino, carboxyl, etc. Thus, “alkyl group”includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls,hydroxyalkyls, sulfoalkyls, etc. On the other hand, the phrase “alkylmoiety” is limited to the inclusion of only pure open chain saturatedhydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl,and the like.

In Formula I, M is a metal selected from the group of niobium andvanadium and X is (NR³R⁴), (PR³R⁴), or (OR⁵), with R¹, R², R³, R⁴, andR⁵ of Formula I being each individually an organic group. Preferably,each of the organic groups of R¹, R², R³, R⁴, and R⁵ contain 1-10 carbonatoms, more preferably, 1-6 carbon atoms, and most preferably, 1-4carbon atoms. Preferably, R² is (CH₂)_(n), with n=1-5.

Additionally, each of the organic groups R¹, R², R³, R⁴, and R⁵ mayoptionally include one or more heteroatoms (e.g., oxygen, nitrogen,fluorine, etc.), or functional groups (e.g., carbonyl groups,hydroxycarbyl groups, aminocarbyl groups, alcohols, fluorinatedalcohols, etc.). That is, included within the scope of the compounds ofFormula I are compounds wherein at least one atom in the organic grouphas been replaced with, for example, one of a carbonyl group, ahydroxycarbyl group, an oxygen atom, a nitrogen atom, or an aminocarbylgroup. Certain preferred organic groups, R¹, R³, R⁴, and R⁵, of FormulaI include (C1-C4) alkyl groups, which may be linear, branched, or cyclicgroups, as well as alkenyl groups (e.g., dienes and trienes), or alkynylgroups.

Examples of precursor compounds of Formula I includeNb(OEt)₄(Me₂NCH₂CH₂O) (also known as niobium tetraethoxydimethylaminoethoxide or NbTDMAE), and Nb(OEt)₄(MeOCH₂CH₂O), wherein Meis methyl, and Et is ethyl.

In addition to the precursor compositions of Formula I, the presentinvention includes methods and apparatus in which a metal containingprecursor compound different that the precursor compound of Formula Imay be used. Such precursors may be deposited/chemisorbed, for examplein an ALD process discussed more fully below, substantiallysimultaneously with or sequentially to the precursor compounds ofFormula I. Further, the different precursor compound may bedeposited/chemisorbed in a deposition cycle either prior to orsubsequently to introducing a reaction gas to the substrate or substrateassembly. These different metal containing precursor compounds maypreferably include at least one metal selected from the group ofbismuth, tantalum, hafnium, aluminum, niobium, vanadium, andcombinations of these metals.

The precursor compounds of the present invention may be preparedaccording to any appropriate method known to one skilled in the art. Forinstance, the precursor may be prepared by reacting a metal alkoxidewith one equivalent of an alcohol having an extra donor function, asillustrated, for example, in the following reaction:Nb(OEt)₅+(HO)R¹NR²R³→Nb(OEt)₄OR¹NR²R³+EtOH

Herein, vaporized precursor compounds may be used either alone oroptionally with vaporized molecules of other precursor compounds oroptionally with vaporized solvent molecules, if used. As used herein,“liquid” refers to a solution or a neat liquid (a liquid at roomtemperature or a solid at room temperature that melts at an elevatedtemperature). As used herein, “solution” does not require completesolubility of the solid but may allow for some undissolved solid, aslong as there is a sufficient amount of the solid delivered by theorganic solvent into the vapor phase for chemical vapor depositionprocessing. If solvent dilution is used in deposition, the total molarconcentration of solvent vapor generated may also be considered as ainert carrier gas.

Solvents that are suitable for some embodiments of the present inventioncan be one or more of the following: aliphatic hydrocarbons orunsaturated hydrocarbons (C3-C20, and preferably C5-C10, cyclic,branched, or linear), aromatic hydrocarbons (C5-C20, and preferablyC5-C10), halogenated hydrocarbons, silylated hydrocarbons such asalkylsilanes, alkylsilicates, ethers, polyethers, thioethers, esters,lactones, ammonia, amides, amines (aliphatic or aromatic, primary,secondary, or tertiary), polyamines, nitrites, cyanates, isocyanates,thiocyanates, silicone oils, alcohols, or compounds containingcombinations of any of the above or mixtures of one or more of theabove. The compounds are also generally compatible with each other, sothat mixtures of variable quantities of the precursor compounds will notinteract to significantly change their physical properties.

The precursor compounds of the present invention can, optionally, bevaporized and deposited/chemisorbed substantially simultaneously with,and in the presence of, one or more reaction gasses. Alternatively, themetal containing layers may be formed by alternately introducing theprecursor compound and the reaction gas(es) during each depositioncycle. Such reaction gasses may typically include oxygen, water vapor,ozone, nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide,hydrogen selenide, hydrogen telluride, hydrogen peroxide, ammonia,organic amine, silane, disilane and higher silanes, diborane, plasma,air, and any combination of these gasses. Preferable optional reactiongasses include oxygen and ozone. A most preferred optional reaction gasis ozone.

Additionally, the precursor compounds can be vaporized in the presenceof one or more inert (i.e., nonreactive) carrier gasses if desired. Suchinert carrier gasses may also be used in purging steps in an ALDprocess, for example. The inert carrier gas typically includes, but isnot limited to, nitrogen, helium, argon, and combinations thereof. Inthe context of the present invention, an inert carrier gas is understoodto be a gas that does not substantially interfere with the formation ofthe metal-containing layer.

The substrate on which the metal oxide layer is formed is preferably asemiconductor substrate or substrate assembly. Any suitablesemiconductor material is contemplated, such as for example,borophosphosilicate glass (BPSG), silicon such as, e.g., conductivelydoped polysilicon, monocrystalline silicon, etc. (for this invention,appropriate forms of silicon are simply referred to as “silicon”), forexample in the form of a silicon wafer, tetraethylorthosilicate (TEOS)oxide, spin on glass (i.e., a thin layer of SiO₂, optionally doped,deposited by a spin on process), TiN, TaN, W, noble metals, etc. Asubstrate assembly may also contain a layer that includes platinum,iridium, rhodium, ruthenium, ruthenium oxide, titanium nitride, tantalumnitride, tantalum-silicon-nitride, silicon dioxide, aluminum, galliumarsenide, glass, etc., and other existing or to-be-developed materialsused in semiconductor constructions, such as dynamic random accessmemory (DRAM) devices and static random access memory (SRAM) devices,for example.

For substrates including semiconductor substrates or substrateassemblies, the layers can be formed directly on the lowestsemiconductor surface of the substrate, or they can be formed on any ofa variety of the layers (i.e., surfaces) as in a patterned wafer, forexample.

Substrates other than semiconductor substrates or substrate assembliescan also be used in methods of the present invention. Any substrate thatmay advantageously form a metal containing layer thereon, such as ametal oxide layer, may be used, such substrates including, for example,fibers, wires, etc.

A preferred deposition process for the present invention is a vapordeposition process. Vapor deposition processes are generally favored inthe semiconductor industry due to the process capability to quicklyprovide highly conformal layers even within deep contacts and otheropenings. Chemical vapor deposition (CVD) and atomic layer deposition(ALD) are two vapor deposition processes often employed to form thin,continuous, uniform, metal-containing (preferably dielectric) layersonto semiconductor substrates. Using either vapor deposition process,typically one or more precursor compounds are vaporized in a depositionchamber and optionally combined with one or more reaction gasses anddirected to and/or contacted with the substrate to form ametal-containing layer on the substrate. It will be readily apparent toone skilled in the art that the vapor deposition process may be enhancedby employing various related techniques such as plasma assistance, photoassistance, laser assistance, as well as other techniques.

Chemical vapor deposition (CVD) has been extensively used for thepreparation of metal-containing layers, such as dielectric layers, insemiconductor processing because of its ability to provide highlyconformal and high quality dielectric layers at relatively fastprocessing times. Typically, the desired precursor compounds arevaporized and then introduced into a deposition chamber containing aheated substrate with optional reaction gasses and/or inert carriergasses in a single deposition cycle. In a typical CVD process, vaporizedprecursors are contacted with reaction gas(es) at the substrate surfaceto form a layer (e.g., dielectric layer). The single deposition cycle isallowed to continue until the desired thickness of the layer isachieved.

Typical CVD processes generally employ precursor compounds invaporization chambers that are separated from the process chamberwherein the deposition surface or wafer is located. For example, liquidprecursor compounds are typically placed in bubblers and heated to atemperature at which they vaporize, and the vaporized liquid precursorcompound is then transported by an inert carrier gas passing over thebubbler or through the liquid precursor compound. The vapors are thenswept through a gas line to the deposition chamber for depositing alayer on substrate surface(s) therein. Many techniques have beendeveloped to precisely control this process. For example, the amount ofprecursor material transported to the deposition chamber can beprecisely controlled by the temperature of the reservoir containing theprecursor compound and by the flow of an inert carrier gas bubbledthrough or passed over the reservoir.

Alternatively, and preferably, the vapor deposition process employed inthe methods of the present invention is a multi-cycle atomic layerdeposition (ALD) process. Such a process is advantageous, in particularadvantageous over a CVD process, in that in provides for improvedcontrol of atomic-level thickness and uniformity to the deposited layer(e.g., dielectric layer) by providing a plurality of deposition cycles.Further, ALD processes typically expose the metal precursor compounds tolower volatilization and reaction temperatures, which tends to decreasedegradation of the precursor as compared to, for example, typical CVDprocesses.

Generally in an ALD process, each reactant is pulsed sequentially onto asuitable substrate, typically at deposition temperatures of about 25° C.to about 400° C. (preferably about 150° C. to about 300° C.). Thesetemperatures are generally lower than those presently used in CVDprocesses, which typically include deposition temperatures at thesubstrate surface in a range of about 100° C. to about 600° C., morepreferably in the range of about 200° C. to about 500° C. Under suchconditions the film growth is typically self-limiting (i.e., when thereactive sites on a surface are used up in an ALD process, thedeposition generally stops), insuring not only excellent conformalitybut also good large area uniformity plus simple and accurate thicknesscontrol. Due to alternate dosing of the precursor compounds and/orreaction gasses, detrimental vapor-phase reactions are inherentlyeliminated, in contrast to the CVD process that is carried out bycontinuous coreaction of the precursors and/or reaction gasses. (SeeVehkamäki et al, “Growth of SrTiO₃ and BaTiO₃ Thin Films by Atomic LayerDeposition,” Electrochemical and Solid-State Letters, 2(10):504-506(1999)).

A typical ALD process includes exposing an initial substrate to a firstchemical species (e.g., a metal precursor compound such as that ofFormula I) to accomplish chemisorption of the species onto thesubstrate. Theoretically, the chemisorption forms a monolayer that isuniformly one atom or molecule thick on the entire exposed initialsubstrate. In other words, a saturated monolayer is substantially formedon the substrate surface. Practically, chemisorption may not occur onall portions of the substrate. Nevertheless, such a partial monolayer isstill understood to be a monolayer in the context of the presentinvention. In many applications, merely a substantially saturatedmonolayer may be suitable. A substantially saturated monolayer is onethat will still yield a deposited layer exhibiting the quality and/orproperties desired for such layer.

The first species is purged from over the substrate and a secondchemical species (e.g., a different precursor compound) is provided toreact with the first monolayer of the first species. The second speciesis then purged and the steps are repeated with exposure of the secondspecies monolayer to the first species. In some cases, the twomonolayers may be of the same species. Optionally, the second speciescan react with the first species, but not chemisorb additional materialthereto. That is, the second species can cleave some portion of thechemisorbed first species, altering such monolayer without forminganother monolayer thereon. Also, a third species or more may besuccessively chemisorbed (or reacted) and purged just as described forthe first and second species. Optionally, the second species (or thirdor subsequent) can include at least one reaction gas if desired.

Thus, the use of ALD provides the ability to improve the control ofthickness and uniformity of metal containing layers on a substrate. Forexample, depositing thin layers of precursor compound in a plurality ofcycles provides a more accurate control of ultimate film thickness. Thisis particularly advantageous when the precursor compound is directed tothe substrate and allowed to chemisorb thereon, preferably furtherincluding at least one reaction gas that reacts with the chemisorbedspecies on the substrate, and even more preferably wherein this cycle isrepeated at least once.

Purging of excess vapor of each species followingdeposition/chemisorption onto a substrate may involve a variety oftechniques including, but not limited to, contacting the substrateand/or monolayer with an inert carrier gas and/or lowering pressure tobelow the deposition pressure to reduce the concentration of a speciescontacting the substrate and/or chemisorbed species. Examples of carriergasses, as discussed above, may include N₂, Ar, He, etc. Additionally,purging may instead include contacting the substrate and/or monolayerwith any substance that allows chemisorption by-products to desorb andreduces the concentration of a contacting species preparatory tointroducing another species. The contacting species may be reduced tosome suitable concentration or partial pressure known to those skilledin the art based on the specifications for the product of a particulardeposition process.

ALD is often described as a self-limiting process, in that a finitenumber of sites exist on a substrate to which the first species may formchemical bonds. The second species might only bond to the first speciesand thus may also be self-limiting. Once all of the finite number ofsites on a substrate are bonded with a first species, the first specieswill often not bond to other of the first species already bonded withthe substrate. However, process conditions can be varied in ALD topromote such bonding and render ALD not self-limiting. Accordingly, ALDmay also encompass a species forming other than one monolayer at a timeby stacking of a species, forming a layer more than one atom or moleculethick.

Thus, during the ALD process, numerous consecutive deposition cycles areconducted in the deposition chamber, each cycle depositing a very thinmetal-containing layer (usually less than one monolayer such that thegrowth rate on average is from about 0.2 to about 3.0 Angstroms percycle), until a layer of the desired thickness is built up on thesubstrate of interest. The layer deposition is accomplished byalternately introducing (i.e., by pulsing) precursor compound(s) intothe deposition chamber containing a substrate, chemisorbing theprecursor compound(s) as a monolayer onto the substrate surfaces,purging the deposition chamber, then introducing to the chemisorbedprecursor compound(s) precursor compound(s) that may be the same as thefirst precursor compound(s) or may be other precursor compound(s) in aplurality of deposition cycles until the desired thickness of themetal-containing layer is achieved. Preferred thicknesses of the metalcontaining layers of the present invention are at least about 10angstroms (Å), and preferably no greater than about 100 Å.

The pulse duration of precursor compound(s) and inert carrier gas(es) isgenerally of a duration sufficient to saturate the substrate surface.Typically, the pulse duration is from about 0.1 second to about 5seconds, preferably from about 0.2 second to about 3 seconds, and morepreferably from about 2 seconds to about 3 seconds.

In comparison to the predominantly thermally driven CVD, ALD ispredominantly chemically driven. Thus, ALD may advantageously beconducted at much lower temperatures than CVD. During the ALD process,the substrate temperature may be maintained at a temperaturesufficiently low to maintain intact bonds between the chemisorbedprecursor compound(s) and the underlying substrate surface and toprevent decomposition of the precursor compound(s). The temperature, onthe other hand, may be sufficiently high to avoid condensation of theprecursor compound(s). Typically the substrate temperature is keptwithin the range of about 25° C. to about 400° C. (preferably about 150°C. to about 300° C., and more preferably about 250° C. to about 300°C.), which, as discussed above, is generally lower than temperaturespresently used in typical CVD processes. Thus, the first species orprecursor compound is chemisorbed at this temperature. Surface reactionof the second species or precursor compound can occur at substantiallythe same temperature as chemisorption of the first precursor or,optionally but less preferably, at a substantially differenttemperature. Clearly, some small variation in temperature, as judged bythose of ordinary skill, can occur but still be considered substantiallythe same temperature by providing a reaction rate statistically the sameas would occur at the temperature of the first precursor chemisorption.Alternatively, chemisorption and subsequent reactions could insteadoccur at substantially exactly the same temperature.

For a typical ALD process, the pressure inside the deposition chamber iskept at about 10⁻⁴ torr to about 10 torr, preferably about 10⁻⁴ torr toabout 1 torr. Typically, the deposition chamber is purged with an inertcarrier gas after the vaporized precursor compound(s) have beenintroduced into the chamber and/or reacted for each cycle. The inertcarrier gas(es) can also be introduced with the vaporized precursorcompound(s) during each cycle.

The reactivity of a precursor compound can significantly influence theprocess parameters in ALD. Under typical CVD process conditions, ahighly reactive compound may react in the gas phase generatingparticulates, depositing prematurely on undesired surfaces, producingpoor films, and/or yielding poor step coverage or otherwise yieldingnon-uniform deposition. For at least such reason, a highly reactivecompound might be considered not suitable for CVD. However, somecompounds not suitable for CVD are superior ALD precursors. For example,if the first precursor is gas phase reactive with the second precursor,such a combination of compounds might not be suitable for CVD, althoughthey could be used in ALD. In the CVD context, concern might also existregarding sticking coefficients and surface mobility, as known to thoseskilled in the art, when using highly gas-phase reactive precursors,however, little or no such concern would exist in the ALD context.

After layer formation on the substrate, an annealing process may beoptionally performed in situ in the deposition chamber in a nitrogenatmosphere or oxidizing atmosphere. Preferably, the annealingtemperature is within the range of about 400° C. to about 1000° C.Particularly after ALD, the annealing temperature is more preferablyabout 400° C. to about 750° C., and most preferably about 600° C. toabout 700° C. The annealing operation is preferably performed for a timeperiod of about 0.5 minute to about 60 minutes and more preferably for atime period of about 1 minute to about 10 minutes. One skilled in theart will recognize that such temperatures and time periods may vary. Forexample, furnace anneals and rapid thermal annealing may be used, andfurther, such anneals may be performed in one or more annealing steps.

As stated above, the use of the complexes and methods of forming filmsof the present invention are beneficial for a wide variety of thin filmapplications in semiconductor structures, particularly those using highdielectric materials. For example, such applications include gatedielectrics and capacitors such as planar cells, trench cells (e.g.,double sidewall trench capacitors), stacked cells (e.g., crown, V-cell,delta cell, multi-fingered, or cylindrical container stackedcapacitors), as well as field effect transistor devices.

A system that can be used to perform vapor deposition processes(chemical vapor deposition or atomic layer deposition) of the presentinvention is shown in FIG. 1. The system includes an enclosed vapordeposition chamber 10, in which a vacuum may be created using turbo pump12 and backing pump 14. One or more substrates 16 (e.g., semiconductorsubstrates or substrate assemblies) are positioned in chamber 10. Aconstant nominal temperature is established for substrate 16, which canvary depending on the process used. Substrate 16 may be heated, forexample, by an electrical resistance heater 18 on which substrate 16 ismounted. Other known methods of heating the substrate may also beutilized.

In this process, precursor compound(s) (such as the precursor compoundof Formula I and optionally metal containing precursor compound(s)different than the precursor compound of Formula I) 60 and/or 61 arestored in vessels 62. The precursor compound(s) are vaporized andseparately fed along lines 64 and 66 to the deposition chamber 10 using,for example, an inert carrier gas 68. A reaction gas 70 may be suppliedalong line 72 as needed. Also, a purge gas 74, which is often the sameas the inert carrier gas 68, may be supplied along line 76 as needed. Asshown, a series of valves 80-85 are opened and closed as required.

FIG. 2 shows an example of the ALD formation of niobium and/orvanadium-containing layers of the present invention as used in anexemplary capacitor construction. Referring to FIG. 2, capacitorconstruction 200 includes substrate 210 having conductive diffusion area240 formed therein. Substrate 210 can include, for example, silicon. Aninsulating layer 260, such as BPSG, is provided over substrate 210, withcontact opening 280 provided therein to diffusion area 240. Conductivematerial 290 fills contact opening 280, and may include, for example,tungsten or conductively doped polysilicon. Capacitor construction 200includes a first capacitor electrode (a bottom electrode) 220, adielectric layer 240 which may be formed by methods of the presentinvention, and a second capacitor electrode (a top electrode) 250.

It is to be understood that FIG. 2 is an exemplary construction, andmethods of the invention are useful for forming niobium oxide layersand/or vanadium oxide layers on any substrate, preferably onsemiconductor structures, and that such applications include capacitorssuch as planar cells, trench cells, (e.g., double sidewall trenchcapacitors), stacked cells (e.g., crown, V-cell, delta cell,multi-fingered, or cylindrical container stacked capacitors), as well asfield effect transistor devices.

Furthermore, a diffusion barrier layer may optionally be formed over thedielectric layer 240, and may, for example, include TiN, TaN, metalsilicide, or metal silicide-nitride. While the diffusion barrier layeris described as a distinct layer, it is to be understood that thebarrier layers may include conductive materials and can accordingly, insuch embodiments, be understood to include at least a portion of thecapacitor electrodes. In certain embodiments that include a diffusionbarrier layer, an entirety of a capacitor electrode can includeconductive barrier layer materials.

The following examples are offered to further illustrate variousspecific embodiments and techniques of the present invention. It shouldbe understood, however, that many variations and modificationsunderstood by those of ordinary skill in the art may be made whileremaining within the scope of the present invention. Therefore, thescope of the invention is not intended to be limited by the followingexample. Unless specified otherwise, all percentages shown in theexamples are percentages by weight.

EXAMPLES Example 1 Deposition of Nb₂O₅ by Atomic Layer Deposition

A Nb₂O₅ film was deposited on a TiN bottom electrode by ALD, asdescribed above, using alternate pulses of Nb(OEt)₄(Me₂NCH₂CH₂O)(NbTDMAE) and ozone (O₃) at a substrate temperature of 325° C. and apressure of 1 Torr. The film was deposited at a rate of 0.35 Å/cycle,with each cycle consisting of a 2 second niobium precursor dose, 4second purge with the inert gas, a 5 second ozone dose (O₃: 500 sccm at15%), and a 15 second purge with the inert gas. An approximately 72 Åthick Nb₂O₅ film resulted.

Example 2 Deposition of Ta/Nb Oxide by Atomic Layer Deposition

Example 1, above, was repeated, with the exception that both TaTDMAE andNbTDMAE precursors were deposited, the deposition rate was 0.425Å/cycle, and an 8 second ozone dose was performed. The niobium appearedto be substantially homogeneously distributed throughout the resultingTa/Nb oxide layer.

The complete disclosures of the patents, patent documents, andpublications cited herein are incorporated by reference in theirentirety as if each were individually incorporated. Variousmodifications and alterations to this invention will become apparent tothose skilled in the art without departing from the scope and spirit ofthis invention. It should be understood that this invention is notintended to be unduly limited by the illustrative embodiments andexamples set forth herein and that such examples and embodiments arepresented by way of example only with the scope of the inventionintended to be limited only by the claims set forth herein as follows.

1. A method of manufacturing a semiconductor structure, the methodcomprising: providing a semiconductor substrate or substrate assembly;providing a vapor comprising at least one precursor compound of theformulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is selected from thegroup consisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or(OR⁵), each R¹, R², R³, R⁴, and R⁵ is independently an organic group,x=1 or 2; and contacting the vapor comprising the at least one precursorcompound of Formula I with the semiconductor substrate or substrateassembly to form a metal-containing layer on at least one surface of thesemiconductor substrate or substrate assembly using an atomic layerdeposition process comprising a plurality of deposition cycles.
 2. Themethod of claim 1 wherein R¹, R², R³, R⁴, and R⁵ are each independentlyorganic groups having 1-10 carbon atoms.
 3. The method of claim 2wherein R² is (CH₂)_(n), wherein n=1-5.
 4. The method of claim 1 whereinthe semiconductor substrate or substrate assembly comprises silicon,borophosphosilicate glass (BPSG), tetraethylorthosilicate (TEOS) oxide,spin on glass, TiN, TaN, W, noble metals, or combinations thereof. 5.The method of claim 1 wherein the metal-containing layer is a metaloxide layer.
 6. The method of claim 1 wherein the metal-containing layeris a dielectric layer.
 7. The method of claim 1 wherein themetal-containing layer has a thickness of about 10 Å to about 100 Å. 8.A method of manufacturing a semiconductor structure, the methodcomprising: providing a semiconductor substrate or substrate assembly;providing a vapor comprising at least one precursor compound of theformulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is selected from thegroup consisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or(OR⁵), each R¹, R², R³, R⁴, and R⁵ is independently an organic group,x=1 or 2; providing at least one reaction gas; and contacting the vaporcomprising the at least one precursor compound of Formula I with thesemiconductor substrate or substrate assembly to form a metal-containinglayer on at least one surface of the semiconductor substrate orsubstrate assembly using an atomic layer deposition process comprising aplurality of deposition cycles.
 9. The method of claim 8 wherein R¹, R²,R³, R⁴, and R⁵ are each independently organic groups having 1-10 carbonatoms.
 10. The method of claim 9 wherein R² is (CH₂)_(n), wherein n=1-5.11. The method of claim 8 wherein the metal-containing layer is a metaloxide layer.
 12. The method of claim 8 wherein the metal-containinglayer is a dielectric layer.
 13. The method of claim 8 wherein the atleast one reaction gas is selected from the group consisting of oxygen,water vapor, ozone, nitrogen oxides, sulfur oxides, hydrogen, hydrogensulfide, hydrogen selenide, hydrogen telluride, hydrogen peroxide,ammonia, organic amine, silane, disilane, higher silanes, diborane,plasma, air, and combinations thereof.
 14. The method of claim 13wherein the at least one reaction gas is selected from the groupconsisting of ozone and oxygen.
 15. The method of claim 8 wherein duringthe atomic layer deposition process, the metal-containing layer isformed by alternately introducing the vapor comprising the at least oneprecursor compound of Formula I and the at least one reaction gas duringeach deposition cycle.
 16. A method of manufacturing a semiconductorstructure, the method comprising: providing a semiconductor substrate orsubstrate assembly within a deposition chamber; providing a vaporcomprising at least one precursor compound of the formulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is selected from thegroup consisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or(OR⁵), each R¹, R², R³, R⁴, and R⁵ is independently an organic group,x=1 or 2; directing the vapor comprising the at least one precursorcompound of Formula I to the semiconductor substrate or substrateassembly and allowing the at least one compound to chemisorb to at leastone surface of the semiconductor substrate or substrate assembly;providing at least one reaction gas; and directing the at least onereaction gas to the semiconductor substrate or substrate assembly withthe chemisorbed species thereon to form a metal-containing layer on atleast one surface of the semiconductor substrate or substrate assembly.17. The method of claim 16 wherein providing a vapor comprising at leastone precursor compound of Formula I, directing the vapor to thesemiconductor substrate or substrate assembly, providing at least onereaction gas, and directing the at least one reaction gas to thesemiconductor substrate or substrate assembly is repeated at least once.18. The method of claim 16 wherein the at least one reaction gas isselected from the group consisting of oxygen, water vapor, ozone,nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide, hydrogenselenide, hydrogen telluride, hydrogen peroxide, ammonia, organic amine,silane, disilane, higher silanes, diborane, plasma, air, andcombinations thereof.
 19. The method of claim 18 wherein the at leastone reaction gas is selected from the group consisting of ozone andoxygen.
 20. The method of claim 16 wherein R¹, R², R³, R⁴, and R⁵ areeach independently organic groups having 1-10 carbon atoms.
 21. Themethod of claim 20 wherein R² is (CH₂)_(n), wherein n=1-5.
 22. Themethod of claim 16 wherein the metal-containing layer is a metal oxidelayer.
 23. The method of claim 16 wherein the metal-containing layer isa dielectric layer.
 24. The method of claim 16 wherein themetal-containing layer has a thickness of about 10 Å to about 100 Å. 25.The method of claim 16 wherein the temperature of the semiconductorsubstrate or substrate assembly is about 25° C. to about 400° C.
 26. Themethod of claim 16 wherein the atomic layer deposition chambercontaining the semiconductor substrate or substrate assembly has apressure of about 10⁻⁴ torr to about 10 torr.
 27. The method of claim 16further comprising purging excess vapor comprising the at least oneprecursor compound of Formula I from the deposition chamber afterchemisorption of the compound onto the semiconductor substrate orsubstrate assembly.
 28. The method of claim 27 wherein purging comprisespurging with an inert gas.
 29. The method of claim 28 wherein the inertgas is selected from the group consisting of nitrogen, helium, argon,and mixtures thereof.
 30. The method of claim 16 further comprisingproviding a vapor comprising at least one metal-containing precursorcompound that is different than the precursor compound of Formula I anddirecting this vapor to the semiconductor substrate or substrateassembly to allow the at least one metal-containing compound tochemisorb on the at least one surface of the semiconductor substrate orsubstrate assembly.
 31. A method of manufacturing a semiconductorstructure, the method comprising: providing a semiconductor substrate orsubstrate assembly; providing a vapor comprising at least one precursorcompound of the formulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is selected from thegroup consisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or(OR⁵), each R¹, R², R³, R⁴, and R⁵ is independently an organic group,x=1 or 2; providing a vapor comprising at least one metal-containingprecursor compound different than M(OR¹)_(5-x)(XR²O)_(x) (Formula I);directing the vapor comprising the at least one precursor compound ofFormula I and the vapor comprising the at least one metal-containingprecursor compound different that the precursor compound of Formula I tothe semiconductor substrate or substrate assembly to form ametal-containing layer on at least one surface of the semiconductorsubstrate or substrate assembly using an atomic layer deposition processcomprising a plurality of deposition cycles.
 32. The method of claim 31wherein R¹, R², R³, R⁴, and R⁵ are each independently organic groupshaving 1-10 carbon atoms.
 33. The method of claim 32 wherein R² is(CH₂)_(n), wherein n=1-5.
 34. The method of claim 31 wherein the vaporcomprising the at least one precursor compound of Formula I and thevapor comprising the at least one metal-containing precursor compounddifferent that the precursor compound of Formula I are directed to thesemiconductor substrate or substrate assembly substantiallysimultaneously.
 35. The method of claim 31 wherein the metal-containinglayer is a metal oxide layer.
 36. The method of claim 31 wherein themetal-containing layer is a dielectric layer.
 37. The method of claim 31further comprising at least one reaction gas.
 38. The method of claim 37wherein the at least one reaction gas is selected from the groupconsisting of oxygen, water vapor, ozone, nitrogen oxides, sulfuroxides, hydrogen, hydrogen sulfide, hydrogen selenide, hydrogentelluride, hydrogen peroxide, ammonia, organic amine, silane, disilane,higher silanes, diborane, plasma, air, and combinations thereof.
 39. Themethod of claim 38 wherein the at least one reaction gas is selectedfrom the group consisting of ozone and oxygen.
 40. The method of claim37 wherein the vapor comprising the at least one precursor compound ofFormula I and the vapor comprising the at least one metal-containingprecursor compound different that the precursor compound of Formula Iare directed to the semiconductor substrate or substrate assembly priorto directing the at least one reaction gas to the semiconductorsubstrate or substrate assembly.
 41. The method of claim 31 wherein thevapor comprising the at least one precursor compound of Formula I andthe vapor comprising the at least one metal-containing precursorcompound different that the precursor compound of Formula I furthercomprise a nonreactive gas.
 42. The method of claim 41 wherein thenonreactive gas is selected from the group consisting of nitrogen,helium, argon, and mixtures thereof.
 43. The method of claim 31 whereinthe metal-containing precursor compound different than Formula Icomprises at least one metal selected from the group consisting ofbismuth, tantalum, hafnium, aluminum, niobium, vanadium, andcombinations thereof.
 44. A method of forming a niobium oxide layer on asubstrate, the method comprising: providing a substrate; providing avapor comprising at least one precursor compound of the formulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is niobium, X is(NR³R⁴), (PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ is independentlyan organic group, x=1 or 2; and contacting the vapor comprising the atleast one precursor compound with the substrate to form a niobium oxidelayer on at least one surface of the substrate using an atomic layerdeposition process comprising a plurality of deposition cycles.
 45. Themethod of claim 44 wherein R¹, R², R³, R⁴, and R⁵ are each independentlyorganic groups having 1-10 carbon atoms.
 46. The method of claim 45wherein R² is (CH₂)_(n), wherein n=1-5.
 47. The method of claim 44wherein the substrate comprises silicon, borophosphosilicate glass(BPSG), tetraethylorthosilicate (TEOS) oxide, spin on glass, TiN, TaN,W, noble metals, or combinations thereof.
 48. The method of claim 44wherein the metal-containing layer is a dielectric layer.
 49. The methodof claim 44 wherein the formed niobium oxide layer has a thickness ofabout 10 Å to about 100 Å.
 50. A method of forming a niobium oxide layeron a substrate, the method comprising: providing a substrate; providinga vapor comprising at least one precursor compound of the formulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is niobium, X is(NR³R⁴), (PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ is independentlyan organic group, x=1 or 2; providing at least one reaction gas; andcontacting the vapor comprising the at least one precursor compound withthe substrate to form a niobium oxide layer on at least one surface ofthe substrate using an atomic layer deposition process comprising aplurality of deposition cycles.
 51. The method of claim 50 wherein R¹,R², R³, R⁴, and R⁵ are each independently organic groups having 1-10carbon atoms.
 52. The method of claim 51 wherein R² is (CH₂)_(n),wherein n=1-5.
 53. The method of claim 50 wherein the metal-containinglayer is a dielectric layer.
 54. The method of claim 50 wherein the atleast one reaction gas is selected from the group consisting of oxygen,water vapor, ozone, nitrogen oxides, sulfur oxides, hydrogen, hydrogensulfide, hydrogen selenide, hydrogen telluride, hydrogen peroxide,ammonia, organic amine, silane, disilane, higher silanes, diborane,plasma, air, and combinations thereof.
 55. The method of claim 54wherein the at least one reaction gas is selected from the groupconsisting of ozone and oxygen.
 56. The method of claim 50 whereinduring the atomic layer deposition process, the niobium oxide layer isformed by alternately introducing the vapor comprising the at least oneprecursor compound and the at least one reaction gas during eachdeposition cycle.
 57. A method of forming a niobium oxide layer on asubstrate, the method comprising: providing a substrate within adeposition chamber; providing a vapor comprising at least one precursorcompound of the formulaM(OR¹)_(5-x)X(XR²O)_(x)   (Formula I), wherein: M is niobium, X is(NR³R⁴), (PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ is independentlyan organic group, x=1 or 2; directing the vapor comprising the at leastone precursor compound of Formula I to the substrate and allowing the atleast one compound to chemisorb to at least one surface of thesubstrate; providing at least one reaction gas; and directing the atleast one reaction gas to the substrate with the chemisorbed speciesthereon to form a niobium oxide layer on at least one surface of thesubstrate.
 58. The method of claim 57 wherein the at least one reactiongas is selected from the group consisting of oxygen, water vapor, ozone,nitrogen oxides, sulfur oxides, hydrogen, hydrogen sulfide, hydrogenselenide, hydrogen telluride, hydrogen peroxide, ammonia, organic amine,silane, disilane, higher silanes, diborane, plasma, air, andcombinations thereof.
 59. The method of claim 58 wherein the at leastone reaction gas is selected from the group consisting of ozone andoxygen.
 60. The method of claim 57 wherein providing a vapor comprisingat least one precursor compound of Formula I, directing the vapor to thesubstrate, providing at least one reaction gas, and directing the atleast one reaction gas to the substrate is repeated at least once. 61.The method of claim 57 wherein R¹, R², R³, R⁴, and R⁵ are eachindependently organic groups having 1-10 carbon atoms.
 62. The method ofclaim 61 wherein R² is (CH₂)_(n), wherein n=1-5.
 63. The method of claim57 wherein the metal-containing layer has a thickness of about 10 Å toabout 100 Å.
 64. The method of claim 57 wherein the temperature of thesubstrate is about 25° C. to about 400° C.
 65. The method of claim 57wherein the atomic layer deposition chamber containing the substrate hasa pressure of about 10⁻⁴ torr to about 10 torr.
 66. The method of claim57 further comprising providing a vapor comprising at least onemetal-containing precursor compound that is different than the precursorcompound of Formula I and directing this vapor to the substrate to allowthe at least one metal-containing compound to chemisorb on the at leastone surface of the substrate.
 67. A method of forming a niobium oxidelayer on a substrate, the method comprising: providing a substrate;providing a vapor comprising at least one precursor compound of theformulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is niobium, X is(NR³R⁴), (PR³R⁴), or (OR⁵), each R¹, R², R³, R⁴, and R⁵ is independentlyan organic group, x=1 or 2; providing a vapor comprising at least onemetal-containing precursor compound different thanM(OR¹)_(5-x)(XR²O)_(x) (Formula I); directing the vapor comprising theat least one precursor compound of Formula I and the vapor comprisingthe at least one metal-containing precursor compound different that theprecursor compound of Formula I to the substrate to form a layercomprising niobium oxide on at least one surface of the substrate usingan atomic layer deposition process comprising a plurality of depositioncycles.
 68. The method of claim 67 wherein R¹, R², R³, R⁴, and R⁵ areeach independently organic groups having 1-10 carbon atoms.
 69. Themethod of claim 68 wherein R² is (CH₂)_(n), wherein n=1-5.
 70. Themethod of claim 67 wherein the vapor comprising the at least oneprecursor compound of Formula I and the vapor comprising the at leastone metal-containing precursor compound different that the precursorcompound of Formula I are directed to the substrate substantiallysimultaneously.
 71. The method of claim 67 wherein the metal-containinglayer is a dielectric layer.
 72. The method of claim 67 furthercomprising at least one reaction gas.
 73. The method of claim 72 whereinthe at least one reaction gas is selected from the group consisting ofoxygen, water vapor, ozone, nitrogen oxides, sulfur oxides, hydrogen,hydrogen sulfide, hydrogen selenide, hydrogen telluride, hydrogenperoxide, ammonia, organic amine, silane, disilane, higher silanes,diborane, plasma, air, and combinations thereof.
 74. The method of claim73 wherein the at least one reaction gas selected from the groupconsisting of ozone and oxygen.
 75. The method of claim 67 wherein thevapor comprising the at least one precursor compound of Formula I andthe vapor comprising the at least one metal-containing precursorcompound different that the precursor compound of Formula I are directedto the substrate prior to directing the at least one reaction gas to thesubstrate.
 76. The method of claim 67 wherein the vapor comprising theat least one precursor compound of Formula I and the vapor comprisingthe at least one metal-containing precursor compound different that theprecursor compound of Formula I further comprise a nonreactive gas. 77.The method of claim 76 wherein the nonreactive gas is selected from thegroup consisting of nitrogen, helium, argon, and mixtures thereof. 78.The method of claim 67 wherein the metal-containing precursor compounddifferent than Formula I comprises at least one metal selected from thegroup consisting of bismuth, tantalum, hafnium, aluminum, niobium,vanadium, and combinations thereof.
 79. A method of manufacturing amemory device structure, the method comprising: providing a substratehaving a first electrode thereon; providing at least one precursorcompound of the formulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is selected from thegroup consisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or(OR⁵), each R¹, R², R³, R⁴, and R⁵ is independently an organic group,x=1 or 2; vaporizing the at least one precursor compound of Formula I;contacting the at least one vaporized precursor compound of Formula Iwith the substrate to chemisorb the compound on the first electrode ofthe substrate; providing at least one reaction gas; contacting the atleast one reaction gas with the substrate with the chemisorbed compoundthereon to form a dielectric layer on the first electrode of thesubstrate; and forming a second electrode on the dielectric layer. 80.The method of claim 79 wherein R¹, R², R³, R⁴, and R⁵ are eachindependently organic groups having 1-10 carbon atoms.
 81. The method ofclaim 80 wherein R² is (CH₂)_(n), wherein n=1-5.
 82. The method of claim79 wherein the at least one reaction gas is selected from the groupconsisting of oxygen, water vapor, ozone, nitrogen oxides, sulfuroxides, hydrogen, hydrogen sulfide, hydrogen selenide, hydrogentelluride, hydrogen peroxide, ammonia, organic amine, silane, disilane,higher silanes, diborane, plasma, air, and combinations thereof.
 83. Themethod of claim 82 wherein the at least one reaction gas is selectedfrom the group consisting of ozone and oxygen.
 84. The method of claim79 wherein the vapor comprising the at least one precursor compound ofFormula I further comprises a nonreactive gas.
 85. The method of claim84 wherein the nonreactive gas is selected from the group consisting ofnitrogen, helium, argon, and mixtures thereof.
 86. An atomic layer vapordeposition apparatus comprising: a deposition chamber having a substratepositioned therein; and at least one vessel comprising at least oneprecursor compound of the formulaM(OR¹)_(5-x)(XR²O)_(x)   (Formula I), wherein: M is selected from thegroup consisting of niobium and vanadium, X is (NR³R⁴), (PR³R⁴), or(OR⁵), each R¹, R², R³, R⁴, and R⁵ is independently an organic group,and x=1 or
 2. 87. The apparatus of claim 86 wherein R¹, R², R³, R⁴, andR⁵ are each independently organic groups having 1-10 carbon atoms. 88.The apparatus of claim 86 wherein R² is (CH₂)_(n), wherein n=1-5. 89.The apparatus of claim 86 further comprising at least one source of atleast one reaction gas.
 90. The apparatus of claim 89 wherein the atleast one reaction gas is selected from the group consisting of oxygen,water vapor, ozone, nitrogen oxides, sulfur oxides, hydrogen, hydrogensulfide, hydrogen selenide, hydrogen telluride, hydrogen peroxide,ammonia, organic amine, silane, disilane, higher silanes, diborane,plasma, air, and combinations thereof.
 91. The apparatus of claim 86further comprising at least one source of an inert gas.
 92. Theapparatus of claim 86 further comprising at least one vessel comprisingat least one metal-containing precursor compound that is different thatthe precursor compound of Formula I.
 93. The apparatus of claim 92wherein the at least one metal-containing precursor compound that isdifferent that the precursor compound of Formula I comprises a metalselected from the group consisting of bismuth, tantalum, hafnium,aluminum, niobium, vanadium, and combinations thereof.